a) Field of the Invention
This invention relates to novel calixarene and oxacalixarene derivatives, to polymers of such derivatives, and to use of the derivatives and the polymers thereof for sequestration of metals.
b) Description of the Related Art
U.S. Pat. No. 4,882,449 Harris et. al. describes nitrogen-containing calixarene derivatives selected from the groups ##STR2## wherein m+n=4, 6 or 8
n=an integer 1-8 PA0 m=an integer 0-7 PA0 x=4, 6 or 8 PA0 R.sup.1 is H, alkyl, aralkyl, alkoxy, aroyl, or alkoyl, PA0 R is aliphatic or aromatic, unsubstituted or substituted, hydrocarbyl containing nitrogen, PA0 R.sup.4 is unsubstituted or substituted hydrocarbyl, carbonyl or aryl; PA0 R.sup.5 and R.sup.6 (which may be the same or different) are hydrogen, or unsubstituted or substituted hydrocarbyl. PA0 n=0-8 PA0 m'.gtoreq.1/2(m'+m") PA0 3.ltoreq.m'+m"+n.ltoreq.8 PA0 if n=0, m'+m".gtoreq.4 PA0 R.sup.3 is H, halogen, or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof and R.sup.3 may be the same or different on each aryl group; PA0 R.sup.1 and R.sup.15 which may be the same or different are H or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof; PA0 R.sup.2 is selected from: PA0 n=0-8 PA0 m'.gtoreq.1/2(m'+m") PA0 3.ltoreq.m'+m"+n.ltoreq.8 PA0 if n=0, m'+m".gtoreq.4 PA0 R.sup.3 is H, halogen, or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof and R.sup.3 may be the same or different on each aryl group; PA0 R.sup.15 is H or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof; PA0 X is selected from ##STR6## wherein R.sup.7 and R.sup.8 which may be the same or different are H or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof; PA0 R.sup.9 is --OH, --NH.sub.2, --NHC(O)NH.sub.2 or --NHAr, wherein Ar is aryl or a substituted derivative thereof, PA0 n' is 0 or 1. PA0 R.sup.3 is hydrocarbyl or substituted hydrocarbyl; PA0 R.sup.10 is an acrylate or methacrylate functional group, n is an integer of 1-8, m is an integer of 0-7 and n+m is 4-8. Such compounds may be polymerised free radically. In particular, U.S. Pat. No. 4,699,966 (and also U.S. Pat. No. 4,642,362 Harris et al) describes the preparation of an acrylated calix(6) arene of the formula ##STR8## and the copolymerization thereof to a copolymer insoluble in common organic solvents. The polymer bound calixarenes of U.S. Pat. No. 4,699,966 are described generally as metal ion sequestrants. However the polymerisable calixarene compounds having acrylate or methacrylate functional groups attached directly to the aryl groups through the phenolic oxygen atoms as described in U.S. Pat. No. 4,699,966 are not particularly efficient at sequestering metals and polymers formed therefrom have little utility as metal sequestrants. PA0 R.sup.11 is H or CH.sub.3. PA0 m.gtoreq.1 PA0 q=an integer 2-10 PA0 a which may be the same or different on each aryl group is 0 or 1; PA0 R.sup.3 is H, halogen, hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof and R.sup.3 may be the same or different on each aryl group; PA0 R.sup.11 is as defined above; PA0 R.sup.12 is hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof, PA0 R.sup.13 is hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof,
That application also describes use of such calixarene derivatives for selectively sequestering transition metals from aqueous mixtures of alkali metals and transition metals.
European Patent Publication No. 0,309,291 (Application No. 88 308 897.3) describes oxacalixarene and calixarene derivatives of the formula III: ##STR3## wherein m'+m"=0-8
R.sup.4 which is H, or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof, ##STR4## wherein R.sup.5 and R.sup.6 which may be the same or different are H, hydrocarbyl, aryl, hydrocarbylaryl, or a substituted derivative thereof, PA1 --OR.sup.1, wherein R.sup.1 is as defined above, PA1 and R.sup.17 which is a residue of hydrocarbyl, aryl or hydrocarbylaryl group or of a substituted derivative thereof providing a bond to another oxacalixarene or calixarene derivative of formula III wherein R.sup.2 is R.sup.17. PA1 or N.sup.12'.sub.2 (wherein R.sup.12' is H, hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof), PA1 or OR.sup.14 (wherein R.sup.14 is hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof including a N-substituted derivative thereof), PA1 or NHNH.sub.2, or NHOH or NHAr (wherein Ar is aryl or a substituted derivative thereof). PA1 or --CH.sub.2 X wherein X is selected from ##STR12## wherein R.sup.7 and R.sup.8 which may be the same or different are H or hydrocarbyl (including a cycloaliphatic ring formed by R.sup.7 and R.sup.8 together), aryl, hydrocarbylaryl or a substituted derivative thereof; PA1 R.sup.9 is --OH, --NH.sub.2, --NHC(O)NH.sub.2 or --NHAr, wherein Ar is aryl or a substituted derivative thereof, and PA1 n' is 0 or 1.
That application also describes use of such compounds for sequestering transition metals such as copper and silver, transition series elements such as manganese, alkaline earth elements such as calcium and magnesium, and Group III elements such as aluminum in addition to alkali metals.
Our co-pending Irish Patent Application No. 3982/89 entitled "Calixarene and Oxacalixarene Derivatives and Use thereof for Sequestration of Metals" describes calixarene and oxacalixarene derivatives of the formula IV: ##STR5## wherein m'+m"=0-8
That application also describes use of such compounds for sequestration of metals.
U.S. Pat. No. 4,699,966 Harris et al describes a polymerisable calixarene compound of the formula ##STR7## where the R.sup.1 groups are the same or different H or hydrocarbyl groups, the R.sup.2 groups are H, hydrocarbyl, --CH.sub.2 C(.dbd.O)OR.sup.3 or --CH.sub.2 C(.dbd.O)R.sup.3 ;